CN107570127A - A kind of graphene-based water-oil separating foamed material and its preparation method and application - Google Patents
A kind of graphene-based water-oil separating foamed material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of graphene-based water-oil separating foamed material and its preparation method and application.The preparation method includes：（1）Perforated foams are impregnated in graphene oxide water solution, dried after taking-up；（2）Again by step（1）The material of acquisition is impregnated in the organic solution containing organohalosilanes, after taking out drying, obtains the graphene-based water-oil separating foamed material.Perforated foams are successively impregnated in graphene oxide water solution and organic solution containing organohalosilanes by the present invention, obtained graphene-based water-oil separating foamed material can selective absorption, enrichment oil slick, the organic efficiency of oil product and organic pollution is high.The present invention is prepared for floating oil collecting device simple in construction, LNAPL original positions extraction device and DNAPL original positions extraction device using graphene-based water-oil separating foamed material, effectively improves the recovering effect of oil product and organic pollution.
Description
Technical field
The present invention relates to environmental protection and Oil Recovery technical field, more particularly to a kind of graphene-based water-oil separating foam
Material and its preparation method and application.
Background technology
With expanding economy, daily life and industrial production are increasingly vigorous for the demand of oils product, it is various not
The congruent and oil product of chemical composition is by extensive production, transport and uses.And oils incident of leakage in above process（Including original
Oil leakage, organic solvent leakage etc.）Increasingly frequently, cause considerable damage to natural environment or even trigger the public prominent of regional area
Send out sexual behavior part.
At present, oil product adsorbing domain is concentrated mainly on as the report of oil absorption material on porous media, for example, it is Americanized
Association《ACS nanometers》（Zhu, Q.; Pan, Q., Mussel-Inspired Direct Immobilization of
Nanoparticles and Application for Oil-Water Separation. Acs Nano 2014, 8 (2),
1402-1409）A kind of preparation method and applications of water-oil separating foam are reported, the research and utilization dopamine is by hundreds of nanometers
Fe3O4 or SiO2 nano-particles be fixed on the stephanoporate framework of commercialization polyurethane foam, realize the hydrophobic oleophilic oil of material
Characteristic, the material can adsorb the oil products of own wt decades of times, but need to squeeze into repeatedly during materials'use
The recovery of row oil product and the regeneration of material, therefore complex operation and material property are decayed with the increase of regeneration times.
Germany《Advanced function material》（Bi, H.; Xie, X.; Yin, K.; Zhou, Y.; Wan, S.; He,
L.; Xu, F.; Banhart, F.; Sun, L.; Ruoff, R. S., Spongy Graphene as a Highly
Efficient and Recyclable Sorbent for Oils and Organic Solvents. Advanced
Functional Materials 2012, 22 (21), 4421-4425.）A kind of grapheme foam is reported to return for oil slick
High concentration graphene oxide is carried out hydro-thermal by the method for receipts, the research first（180 DEG C, 24 hours）Then take out and obtained after freezing
Column grapheme foam, the various oil slick of 5000 times of own wts can be directly adsorbed, should because pure Carbon Materials do not possess elasticity
Report using heating method carry out oil product distillation recovery, this method not only consume energy it is high and also it is cumbersome do not possess it is too big
Actual application value.
Patent CN103613799 reports a kind of preparation method of oil absorption polyurethane foam, and this method first passes through foaming
Polyurethane foam is prepared, then its surface is modified using tung oil or organosilicon to obtain high oil absorption multiplying power, low water suction times
The foamed material of rate, this method need also exist for carrying out the recovery of oil product and the regeneration of material, operating process using mechanical presses
It is difficult to amplify；It is that a kind of high cost ineffective rate realizes Oil Recovery and the mode of material regeneration.
At the same time, in groundwater remediation field, the technology for repairing NAPLs in water table at present is not by pollutant
Extracted out with together with underground water, carry out dystopy processing；Exactly adding medicament, either microorganism etc. is removed by chemistry or biological respinse
Remove underground pollution thing.These technical schemes are not only complicated, and running cost is high, time-consuming longer, and the treatment effect of some methods
It is unsatisfactory until now.
Such as：The U of patent CN 201634455 report chlorinated hydrocarbon nonaqueous phase liquid in a kind of extraction polluted underground water
Easy device, NAPLs can be evacuated to by ground by manual operation hand-press water pump, to carry out subsequent treatment or load container,
This method belongs to pollutant is extracted out after the method that handles of dystopy, and pollutant is not implemented and is directly separated.
The A of patent CN 104307857 report electric power control and the repair system of nonaqueous phase liquid pollutant in soil
And method, this method are aided with the solubilization of surfactant, pollute produce to nonaqueous phase by applying non-homogeneous frequency conversion electric field
Raw electric osmose, electrophoresis and dielectrophoresis effect, to reach the solubilising to nonaqueous phase liquid pollutant in soil and groundwater, control is moved
Move, the purpose for being finally enriched with and removing.This method complex operation and less efficient, the pollutant after enrichment also needs to be collected
Processing.
The A of patent CN 105399193 report the compound chlorohydrocarbon of heavy non-aqueous liquid composition in a kind of degraded underground water
The method of pollution, the mixed liquor of sodium peroxydisulfate and sodium hydroxide is added in the water body containing compound chlorinated hydrocarbon contaminants and degraded
Repair, this method belongs to chemical remediation category and needs to use a large amount of chemical agents, and is also easy to produce secondary pollution.
Patent 200680052554.X reports the method and equipment for repairing contaminated land, this method first definitely under
Nonaqueous phase liquid（NAPL）Position, then remove pollutant by supplying oxygen burning, this method by being flared off pollutant,
Often cause secondary pollution.
However, substantially, the NAPLs in soil or underground water falls within the category of leakage oil product, therefore, can introduce oil
The theory and method of product recovery, NAPLs is turned waste into wealth, realizes the recycling of pollutant.
The content of the invention
For the above-mentioned problems in the prior art, object of the present invention is to provide a kind of graphene-based profit point
From foamed material and its preparation method and application.The graphene-based water-oil separating foam material specially prepared using this method
Material and the material by floating oil collecting device, LNAPL original positions extraction device, DNAPL original positions extraction device in Oil Recovery, soil
With the application in the organic pollution recovery of underground water.The graphene-based water-oil separating foamed material has super oleophylic super-hydrophobic
Characteristic, can selective absorption and enrichment the water surface oil slick, oil product and organic pollution, realize close to 100%（All tests
It is all higher than 99%）High organic efficiency.
A kind of described graphene-based water-oil separating foamed material, it is characterised in that graphene-based water-oil separating foamed material
Contact angle be 120-155 degree, it is impregnated in graphene oxide water solution by perforated foams, containing organohalosilanes successively
Drying obtains after organic solution, and the foamed material skeleton has a cavity structure closely arranged, cavities open outwardly it is tightly packed
Together, its internal diameter is 1-2 microns, and the foam surface material includes graphene oxide and SiOx materials, and there is super oleophylic to surpass
Hydrophobic property, the x in SiOx are 1 or 2.
The preparation method of described graphene-based water-oil separating foamed material, it is characterised in that comprise the following steps：
1）Perforated foams are impregnated in graphene oxide water solution, further take out drying；
2）By step 1）The material of acquisition is impregnated in the organic solution containing organohalosilanes, is further taken out drying and is obtained the graphite
Alkenyl water-oil separating foamed material.
Porous foam is impregnated in graphene oxide by the present invention（GO）In the aqueous solution, after taking out drying, the table of porous foam
Face can form one layer of graphene oxide layer, the oxygen-containing functional group meeting of the graphene oxide layer surface and organohalosilanes（As thin
Water treatment agent）Chemically react, generate covalent bond；At the same time, after impregnating the organic solution containing organohalosilanes, drying
When, hydrolytic crosslinking reaction can occur with the moisture in air for organohalosilanes, finally be formed on porous foam surface super-hydrophobic
Organosilan cross-linked network structure.The special micro and nano structure possessed due to the hydrophobic property and material of organosilan it is common
Effect, obtained modified porous foam have super-hydrophobicity.
The preparation method of described graphene-based water-oil separating foamed material, it is characterised in that step 1）In porous foam
Material is polyurethane foam, melamine foams, polyvinyl alcohol foam or foam metal；The foam metal be nickel foam, foam copper,
Any one in foamed aluminium or foamed iron, preferably nickel foam.
The preparation method of described graphene-based water-oil separating foamed material, it is characterised in that step 1）In graphite oxide
The concentration of graphene oxide is 0.01 ~ 1mg/mL in aqueous solution, and the effect of graphene oxide of the present invention is in porous foam base
One layer of graphene oxide transition zone, abundant oxygen-containing functional group meeting and organohalosilanes due to surface of graphene oxide are formed on bottom
Reaction, so when graphene oxide concentration is too high, graphene oxide layer is too thick to cause waste of material, and 0.01- is only needed in the present invention
1mg/ml graphene oxide concentration can form one layer of graphite oxide transition zone on porous substrate material surface, realize material
Structure growth control process.
The preparation method of described graphene-based water-oil separating foamed material, it is characterised in that step 1）In dipping when
Between be 0.5 ~ 2h, preferably 1h；The temperature of drying is 50 ~ 70 DEG C, and preferably 50 ~ 60 DEG C, the time of drying is 3 ~ 10h, preferably
For 3 ~ 8h.The present invention specifically defines technical parameter, and the dip time such as limited most elects 1h as, is advantageous to stannic oxide/graphene nano
Piece is fully deposited on perforated foams by intermolecular force or physisorption；Drying temperature is for material
Prepare it is most important, because graphene oxide performance containing abundant oxygen-containing functional group is advantageous to subsequent chemical reaction, drying temperature
It is too high, oxygen-containing functional group can be caused to remove, temperature is too low, and drying time is oversize；If the drying temperature limited is 60 DEG C, during drying
Between be 5h；5 h are dried at 60 DEG C material can be dried, while retain the abundant oxygen-containing functional group of surface of graphene oxide, are had
Beneficial to the reaction of follow-up organohalosilanes.
The preparation method of described graphene-based water-oil separating foamed material, the mass concentrations of organohalosilanes for 0.1 ~
10wt%, the organohalosilanes are organochlorosilane or organic iodine silane, and organochlorosilane is octadecyl trichlorosilane alkane, uncle
Butyldimethylchlorosilane, tri isopropyl chlorosilane, phenyl trichlorosilane, tert-butyl chloro-silicane, trim,ethylchlorosilane,
Dimethyldichlorosilane or methyl trichlorosilane, preferably octadecyl trichlorosilane alkane, phenyl trichlorosilane, trimethylchloro-silicane
Alkane, dimethyldichlorosilane or methyl trichlorosilane, optimal is methyl trichlorosilane；Organic iodine silane is Iodotrimethylsilane.
The preparation method of described graphene-based water-oil separating foamed material, it is characterised in that step 2）In dipping when
Between be 2 ~ 20min, preferably 2 ~ 10min；Drying temperature is 10 ~ 30 DEG C, preferably 20 ~ 30 DEG C；The time of drying is 1 ~ 3h, excellent
Elect 30 ~ 60min, step 2 of the present invention as）Dipping process in organohalosilanes in organic solution can be with porous material surface
Graphene oxide chemically reacts, and generates firm covalent bond（The process chemistry kinetics is rapid, 2 ~ 10min
Complete）, then porous material is taken out, dried, the moisture in drying process in the organohalosilanes and air on material material surface
React, cellular micro nano structure is formed in porous material substrate.
Described graphene-based water-oil separating foamed material is former in Oil Recovery and soil and groundwater organic pollution
Application in the reparation of position.
The floating oil collecting device of described graphene-based water-oil separating foamed material.
Described floating oil collecting device, including graphene-based water-oil separating foamed material, first gear pump, oil pipe and oil slick
Graphene-based water-oil separating foam interior is inserted in collection vessel, first gear pump one end by oil pipe, and the other end passes through oil
Pipe connects with collection vessel, and graphene-based water-oil separating foamed material can carry out oil slick receipts directly as the absorption plant of oil slick
Collection, can also be processed further that the absorption plant for being filled with the graphene-based water-oil separating foamed material is made；The foamed material
Can be the arbitrary shape such as square, circular, the floating oil collecting device is used to be placed in ship to work.
The LNAPL original positions extraction device or DNAPL original positions extraction device of described graphene-based water-oil separating foamed material,
Organic Contamination of Groundwater is LNAPL pollutants and DNAPL pollutants, LNAPL original positions extraction device or DNAPL original positions extraction device
It is respectively used to handle LNAPL pollutants and DNAPL pollutants.
LNAPL original positions extraction device, including：LNAPL in LNAPL Polluted areas collects well, positioned at LNAPL
The ground water recharging well of Polluted area upstream, go deep into LNAPL and collect the underground water being connected in well and ground water recharging well with water pump
Extraction line, and for extracting the collection device of LNAPL pollutants；The collection device is by graphene-based water-oil separating foam material
Material, second gear pump, oil pipe and LNAPL collection vessels composition；Wherein, oil pipe inserts one end and is inserted into graphene-based water-oil separating
The foam interior other end is connected by oil pipe with second gear pump intake, the second gear pump discharge by oil pipe with
LNAPL coated lycopenes are led to.
DNAPL original positions extraction device, including：DNAPL in DNAPL Polluted areas collects well and for extracting
The collection device of DNAPL pollutants, the collection device by graphene-based water-oil separating foamed material, oil pipe, second gear pump, enter
Tracheae, air blower and DNAPL collection vessels composition；Wherein, graphene-based water-oil separating foam material is inserted in one end of the oil pipe
In material, the other end is connected with second gear pump intake；The second gear pump discharge passes through oil pipe and DNAPL collection vessel phases
Connection；In addition, being also inserted with air inlet pipe in graphene-based water-oil separating foamed material, and it is connected by air inlet pipe with air blower.
The graphene base oil used in the collection device of above-mentioned LNAPL original positions extraction device and DNAPL original positions extraction device
Water separation foamed material can carry out the collection of organic pollution directly as the absorption plant of organic pollution, can also enter one
Step is processed into the absorption plant for being filled with the graphene-based water-oil separating foamed material；The foamed material can be square, circle
The arbitrary shapes such as shape.
By using above-mentioned technology, compared with prior art, the invention has the advantages that：
1）Perforated foams are successively impregnated in graphene oxide water solution and the organic solution containing organohalosilanes by the present invention
In, obtained graphene-based water-oil separating foamed material being capable of selective absorption, enrichment oil slick and organic pollution so that
The organic efficiency of oil product and organic pollution is high；
2）The present invention is prepared for floating oil collecting device simple in construction using graphene-based water-oil separating foamed material, significantly reduces
Manufacturing cost, and will not produce a large amount of adsorbents（Such as activated carbon, fiber cloth, sponge etc.）Waste material；Filled using the floating oil collecting
Put the oil slick for collecting same volume, 1 percent of its running cost less than existing oil-absorbing ship or oil skimmer；
3）The floating oil collecting device of the present invention has the ability of serialization high efficiente callback leakage oil product, when second gear pump is opened
Afterwards, the present apparatus can with continuity from the water surface skimming, compared with traditional absorption method, absorbency capacity is not only restricted to adsorbent
Volume and weight, a large amount of oil absorption materials are saved during use, there is higher Oil Recovery efficiency；
4）The LNAPL original positions extraction device of the present invention because of the super-hydrophobic graphene-based water-oil separating foamed material of super oleophylic of arranging in pairs or groups,
There is high selectivity to the LNAPL in soil and underground water, specific can absorb LNAPL into the foamed material of the present invention,
Then LNAPL is continuously extracted out under the driving of second gear pump；
5）The LNAPL original positions extraction device of the present invention is used to LNAPL is extracted out and reclaimed, and is advantageously implemented the money of pollutant
Sourceization recycles, and compared with conventional chemical methods, not only treatment effeciency greatly improves, and without using any chemical agent, to ring
The infringement in border is reduced to minimum；The device is prepared simply, and compared with traditional LNAPL method for extracting and equipment, its cost is cheap,
It is easy to operate, it is easy to maintenance, it is suitable for commercially producing and the reparation of contaminated site；Because the device combination second gear pump enters
Row continuous operation, so the disposal ability of apparatus of the present invention is not limited by material volume or weight, the operation bullet of equipment
Big, the LNAPL site remediations available for various scales of property；
6）The DNAPL original positions extraction device of the present invention because of the super-hydrophobic graphene-based water-oil separating foamed material of super oleophylic of arranging in pairs or groups,
There is high selectivity to the DNAPL of water table bottom, DNAPL specific can be absorbed into material, then in second gear
DNAPL is continuously extracted out under the driving of pump；Device is prepared simply, easy to operate, easy to maintenance.
Brief description of the drawings
Fig. 1 a are to amplify 200 times under the SEM that embodiment 1 is graphene-based water-oil separating foamed material
Photo；
Fig. 1 b are the scanning that embodiment 1 is the porous micro nano structure that graphene-based water-oil separating foamed material skeleton surface obtains
Electron micrograph；
Fig. 1 c are that embodiment 1 is the another of the porous micro nano structure that graphene-based water-oil separating foamed material skeleton surface obtains
Electron scanning micrograph；
Fig. 1 d are the high magnification numbe electron scanning micrograph of graphene-based water-oil separating foam surface micro nano structure；
Fig. 2 is the Fourier infrared spectrum figure of graphene-based water-oil separating foamed material in embodiment 1；
Fig. 3 is the X ray diffracting spectrum of graphene-based water-oil separating foamed material in embodiment 1；
Fig. 4 is the x-ray photoelectron energy spectrum diagram of graphene-based water-oil separating foamed material in embodiment 1；
Fig. 5 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 1；
Fig. 6 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 2；
Fig. 7 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 3；
Fig. 8 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 4；
Fig. 9 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 5；
Figure 10 is the weightening result figure that graphene-based water-oil separating foamed material adsorbs after variety classes oil product in embodiment 6；
Figure 11 is the structural representation of the floating oil collecting device in application examples 1；
Figure 12 is the oil pumping rating results when floating oil collecting device in application examples 2 carries out water surface diesel oil collection experiment in 10 hours
Figure；
Figure 13 is the structural representation of the LNAPL original positions extraction device in application examples 3；
Figure 14 is the structural representation of DNAPL original positions extraction device in application examples 5.
In figure：The graphene-based water-oil separating foamed materials of 1-, 2- oil pipes, 3- first gear pumps, 4- floating oil collecting containers, 5-
Ship；6- groundwater extraction pipelines, 7- ground water recharging wells, 8- water pumps, 9-LNAPL collect well, 10- second gear pumps, 11-
LNAPL collection vessels, 12- air blowers, 13- air inlet pipe, 14-DNAPL collection vessels, 15-DNAPL collect well, 16- earth's surfaces, 17-
Basement rock.
Embodiment
The present invention is done with reference to Figure of description and specific embodiment and further illustrated.
Graphene oxide dispersion used in following examples of the present invention（That is graphene oxide water solution）Preparation side
Method（Improved Hummers methods）Specially：
（1）Low-temp reaction：First 15 g graphite powders and 7 g sodium nitrate are added in the 460 ml concentrated sulfuric acids, 2 are stirred under condition of ice bath
H, then by 50 g KMnO4（KMnO4 particles are clayed into power in advance）It is slowly added into reaction system（Added in 45 min,
Temperature of reaction system maintains 5 ~ 8 DEG C）.
（2）Medium temperature is reacted：By step（1）Reaction solution be transferred in 35 DEG C of water-baths, lasting stirring, react 1 h.
（3）Pyroreaction：Water-bath pot temperature is adjusted to 98 DEG C, while 500 ml water are slowly added to step（2）In not
In the sticky reaction system of disconnected stirring；After adding water, temperature stabilization reacts 30 min at 98 DEG C；After the pyroreaction stage terminates,
The complete potassium permanganate of unreacted is removed with 10 ml hydrogen peroxide, and stirs 1 h.
（4）After completion of the reaction, obtained graphene oxide is cleaned into neutrality using centrifugal cleaning machine, loads 1L silk mouth bottles
In, graphene oxide original liquid concentration is demarcated, and obtain the graphene oxide dispersion of certain concentration.
It is specific as follows：Take the graphene oxide stoste of 50 mL unknown concentrations, after freeze-drying, its solid masses is referred to as
325 mg, the concentration for calculating native oxide graphene are 6.5 mg/mL；461.6 mL native oxides graphenes are taken in 500 mL
In volumetric flask, appropriate amount of deionized water constant volume is added to 500mL, that is, obtains the graphene oxide that demarcation concentration is 6 mg/mL and disperses
Liquid.So far, high concentration graphene oxide dispersion is prepared and finished.
In experimentation, the graphene oxide of extra fine quality can be obtained by measuring certain volume graphene oxide stoste
Dispersion liquid, it so can rapidly and accurately obtain the graphene oxide dispersion of certain concentration.This configuration graphene oxide point
The method of dispersion liquid eliminates cumbersome weighing during Conventional solid graphene oxide Feedstock treating and ultrasonic disperse step.
Embodiment 1
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
1）The melamine foams that specification is 3cm × 3cm × 3cm are placed in the graphene oxide water solution that concentration is 0.5mg/mL and soaked
After steeping 1h, take out, oven drying 5h at 60 DEG C；
2）Again by step 1）In obtained material be placed in the hexane solution for the methyl trichlorosilane that volume fraction is 0.1% and soak
2min is steeped, 35 degrees Celsius of drying 1h, obtain graphene-based water-oil separating foamed material after taking-up.
Electron microscope, X-ray diffraction, X ray photoelectricity are scanned to above-mentioned graphene-based water-oil separating foamed material
The microstructures such as sub- power spectrum, Raman spectrum and surface chemistry are characterized as shown in Fig. 1 ~ 4.
As Fig. 1 a, Fig. 1 b, Fig. 1 c and Fig. 1 d scanning electron microscope image shown in, foamed material manufactured in the present embodiment
The cavity structure closely arranged is grown on skeleton, cavities open is closely packed together outwardly, and its internal diameter is about 1-2 microns；
Such as Fig. 2 Fourier infrared spectrum（FTIR）Shown in figure, it can be seen that material surface contains the functional groups such as N-H, C-H, O-H
Deformation vibrations and C-N, C-Cl functional group flexible vibrations；
The X-ray diffraction as corresponding to Fig. 3（XRD）The bright material surface of chart mainly contains graphene oxide and SiOx（X=1,2)）
Material；
As shown in figure 4, further x-ray photoelectron power spectrum（XPS）Sign it is apparent that the material surface Si, the C that contain,
The elements such as N, O.
As shown in figure 5, absorption spirogram of the graphene-based water-oil separating foamed material of embodiment 1 to variety classes oil product,
The weightening ratio kg/kg of quality of materials after different oil products is adsorbed in expression in figure, and as can be seen from the figure embodiment 1 is graphene-based
Water-oil separating foamed material has very big adsorption capacity, and its structure assigns the super oleophylic superhydrophobic characteristic of material, while determines the material
The contact angle of material water is up to 154 degree.
Embodiment 2
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
1）The polyurethane foam that specification is 3cm × 3cm × 3cm is placed in the graphene oxide water solution that concentration is 1mg/mL and soaked
After steeping 1h, extruded 2 times after taking-up, the most of moisture for the middle absorption that defoams, the oven drying 5h at 60 DEG C；
2）Again by step 1）In obtained material be placed in the acetone soln for the methyl trichlorosilane that volume fraction is 0.2% and soak
2min, 25 DEG C of drying 1h, obtain graphene-based water-oil separating foamed material after taking-up.
The contact angle of the graphene-based water-oil separating foamed material is 148 degree；Its adsorbance to variety classes oil product, such as
Shown in Fig. 6.
Embodiment 3
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
（1）It is water-soluble that the polyvinyl alcohol foam that specification is 3cm × 3cm × 3cm is placed in the graphene oxide that concentration is 0.1mg/mL
After soaking 1h in liquid, take out, oven drying 8h at 50 DEG C；
（2）Again by step（1）In obtained material be placed in the octadecyl trichlorosilane alkane that volume fraction is 0.1% n-hexane it is molten
10min is soaked in liquid, 25 DEG C of drying 3h, obtain graphene-based water-oil separating foamed material after taking-up.
The contact angle of the graphene-based water-oil separating foamed material is 128 degree；Its adsorbance to variety classes oil product, such as
Shown in Fig. 7.
Embodiment 4
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
1）The nickel foam that specification is 3cm × 3cm × 3cm is placed in the graphene oxide water solution that concentration is 0.1mg/mL and soaked
After 1h, take out, oven drying 3h at 50 DEG C；
2）Again by step 1）In obtained material be placed in the hexane solution for the phenyl trichlorosilane that volume fraction is 0.3% and soak
10min is steeped, 25 DEG C of drying 3h, obtain graphene-based water-oil separating foamed material after taking-up.
The contact angle of the graphene-based water-oil separating foamed material is 135 degree；Its adsorbance to variety classes oil product, such as
Shown in Fig. 8.
Embodiment 5
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
1）The melamine foams that specification is 3cm × 3cm × 3cm are placed in the graphene oxide water solution that concentration is 0.2mg/mL and soaked
After steeping 1h, take out, oven drying 4h at 50 DEG C；
2）Again by step 1）In obtained material be placed in the dimethyldichlorosilane hexane solution that volume fraction is 2% and soak
20min, 30 DEG C of drying 2h, obtain graphene-based water-oil separating foamed material after taking-up.
The contact angle of the graphene-based water-oil separating foamed material is 139 degree；Its adsorbance to variety classes oil product, such as
Shown in Fig. 9.
Embodiment 6
A kind of preparation method of graphene-based water-oil separating foamed material, is comprised the following steps that：
1）The polyurethane foam that specification is 3cm × 3cm × 3cm is placed in the graphene oxide water solution that concentration is 0.2mg/mL
After soaking 1h, take out, oven drying 4h at 50 DEG C；
2）Again by step 1）In obtained material be placed in the acetone soln for the trim,ethylchlorosilane that volume fraction is 2% and soak
20min, 30 DEG C of drying 2h, obtain graphene-based water-oil separating foamed material after taking-up.
The contact angle of the graphene-based water-oil separating foamed material is 126 degree；Its adsorbance to variety classes oil product, such as
Shown in Figure 10.
Application examples 1
The application example uses graphene-based water-oil separating foamed material in embodiment 1 to be prepared into floating oil collecting device, is specially：
As shown in figure 11, the floating oil collecting device used in skimming, including graphene-based water-oil separating foamed material 1, first
Graphene-based water-oil separating foam is inserted in gear pump 3, oil pipe 2 and floating oil collecting container 4, the one end of first gear pump 3 by oil pipe 2
Inside material 1, the other end is connected by oil pipe 2 with floating oil collecting container 4, and graphene-based water-oil separating foamed material 1 can be straight
Connect and carry out floating oil collecting as the absorption plant of oil slick, can also be processed further being made and be filled with the graphene-based water-oil separating
The absorption plant of foamed material；The foamed material can be the arbitrary shape such as square, circular, and the floating oil collecting device is used to place
Worked in ship 5, first gear pump 3 used is self-priming first gear pump in the embodiment of the present invention.
Oil slick removal process is as follows：By oil pipe 2（Internal diameter 6mm, external diameter 8mm）Graphene-based water-oil separating foam is inserted in one end
In material 1, and sealed and fixed with epoxy resin；Again by the other end of oil pipe 2 and first gear pump 3（12V, 15W）Entrance is connected, the
The outlet of one gear pump 3 is connected by oil pipe 2 with floating oil collecting container 4, for being collected to oil slick；The device works
30 second time, i.e., 100ml viscous crude oils are reclaimed from the water surface, without extracting any moisture.
Application examples 2
The application example uses graphene-based water-oil separating foamed material in embodiment 2 to be prepared into floating oil collecting device, is specially：
By PVC transparent pipe（Internal diameter 3mm, external diameter 5mm）As oil pipe 2, one end is inserted into graphene-based water-oil separating foamed material 1
In, and sealed and fixed with epoxy resin；Again by the other end and gear pump of oil pipe 2（3V, 15W）Porch be connected, gear pump
Outlet be connected again by PVC transparent pipe with floating oil collecting container 4, so as to form floating oil collecting device.The floating oil collecting fills
Putting to be placed in ship, and for the collection of oil slick, embodiment is entered using above-mentioned floating oil collecting device to water surface organic solvent
Row is collected；70 second time, i.e., 100ml water surface diesel oil is fully drawn out, without extracting any moisture.
In addition, the collection that floating oil collecting device is carried out to long-time water surface diesel oil is tested, it can be found that by 10 hours even
After continuous work, efficiency is still kept, and has no decay, as shown in figure 12, illustrates that the device can be used for long-time water surface oil product
Recovery operation.
Application examples 3
The application example uses graphene-based water-oil separating foamed material in embodiment 2 to prepare LNAPL original positions extraction device progress ground
The in-situ immobilization work of lower water LNAPL pollutions.
As shown in figure 13, the LNAPL original positions extraction device used in the present embodiment, is arranged between earth's surface 16 and basement rock 17,
Underground water upstream is the left side, and downstream is the right, and the device includes：LNAPL in LNAPL Polluted areas collects well 9, is located at
The ground water recharging well 7 of LNAPL Polluted areas upstream, go deep into LNAPL and collect in well 9 and ground water recharging well 7 and connect with water pump 8
The groundwater extraction pipeline 6 connect, and for extracting the collection device of LNAPL pollutants；The collection device is by graphene base oil
Water separation foamed material 1, second gear pump 10, oil pipe 2 and LNAPL collection vessels 11 form；Wherein, the one end of oil pipe 2 is inserted into
Inside graphene-based water-oil separating foamed material 1, the other end connects with the entrance of second gear pump 10, and the second gear pump 10 goes out
Mouth is connected by oil pipe 2 with LNAPL collection vessels 11.
The graphene-based water-oil separating foamed material 1 that the device uses can be directly as the absorption plant of organic pollution
The collection of organic pollution is carried out, can also be processed further that the suction for being filled with the graphene-based water-oil separating foamed material is made
Receiving apparatus；The foamed material can be the arbitrary shape such as square, circular.
Its method is as follows：The LNAPL original positions extraction device in the process of running, by collection device by LNAPL collect to
In LNAPL collection vessels 11, and underground water is then transported into ground water recharging well 7 by water pump 8 through groundwater extraction pipeline 6,
So as to realize the separation of pollutant and underground water；Area of low pressure can be formed centered on LNAPL collection wells 9, in hydraulic action
Lower its periphery underground water and LNAPL can continually flow to LNAPL and collect well, be collected so as to form LNAPL serialization, together
When underground water circulated in underground, without being extracted.
The borehole wall that LNAPL in the embodiment collects well 9 is porous self-supporting material, the circle formed such as stainless (steel) wire
The borehole wall, or pvc pipe, PE pipes, steel pipe directly from surface drilling, ensure that LNAPL can be smoothly flowed into and collect in well
It is collected device to absorb and be enriched with, due to the super oleophylic super-hydrophobicity of graphene-based water-oil separating foamed material, second gear
The device realizes being directly separated and extracting for LNAPL under the driving of pump.
The manufacture of the LNAPL original positions extraction device and maintenance cost are relatively low, without being equipped with complicated instrument and automation
Equipment, operating process is easy, the high efficiente callback of LNAPL pollutants in soil can be realized, because most LNAPL belongs to stone
Oils organic matter, the LNAPL in collection vessel can be sent to oil plant or oil product processing enterprise as life directly as raw material
Raw material is produced, therefore this method also achieves the process that the recovery of LNAPL pollutants is changed into the energy, there is optimal economic benefit.
Application examples 4
The extractive process that the application example pollutes according to the principle simulation soil of above-mentioned application examples 3 with the LNAPL in water table.
Quartz sand is first inserted in a model, and centre is supported to form LNAPL collection wells 9 with stainless (steel) wire, while is received in LNAPL
Collect the both sides of well 9 and be embedded to two drinking-water pipes, water pipe is connected with water pump 8, the outlet guide of water pump 8 to LNAPL upstreams, then sequentially adds certainly
Water and n-hexane（Simulate LNAPL）, forming the LNAPL polluted underground waters of simulation, it can be seen that and LNAPL layers are darker regions,
In water layer upper end.
After drinking-water pipe is opened, LNAPL collects the bottom aqueous layer of well 9 and reduced, and LNAPL upstreams water layer is thickening, in Action of Gravity Field
Aqueous phase in lower water table continually collects Jing Chu flowings because water table change causes LNAPL layers to middle LNAPL
Collecting, thickness at well is maximum, is influenceed by water table flowing, LNAPL continually flows to middle LNAPL and collects well.
By the graphene-based water-oil separating foamed material for being inserted with oil pipe be put into LNAPL collect well, then can continually by
LNAPL in water table is carried out extraction in situ by ground, and due to the particularity that the hydrology flows in underground water, the LNAPL in device is passed through
Crossing 1h can just be fully drawn out.Finally, it can be found that after LNAPL is extracted in underground water, graphene-based water-oil separating foam material
Material is floated on above water layer, only extracts air without withdrawing moisture.
Application examples 5
The application example uses the graphene-based water-oil separating foamed material in embodiment 2 to prepare DNAPL original positions extraction device and carried out
The in-situ immobilization work of underground water DNAPL pollutions.
As shown in figure 14, the DNAPL original positions extraction device used in the embodiment, is arranged between earth's surface 16 and basement rock 17,
Underground water upstream is the left side, and downstream is the right, and medium line is phreatic line, including：In DNAPL Polluted areas
DNAPL collects well 15 and the collection device for extracting DNAPL pollutants, and the collection device is by graphene-based water-oil separating foam
Material 1, oil pipe 2, second gear pump 10, air inlet pipe 13, air blower 12 and DNAPL collection vessels 14 form；Wherein, the oil pipe
2 one end are inserted in graphene-based water-oil separating foamed material 1, and the other end is connected with the entrance of second gear pump 10；Described second
The outlet of gear pump 10 is connected by oil pipe 2 with DNAPL collection vessels 14；In addition, in graphene-based water-oil separating foamed material 1
Air inlet pipe 13 is also inserted with, and is connected by air inlet pipe 13 with air blower 12.
The graphene-based water-oil separating foamed material used in the collection device of above-mentioned DNAPL original positions extraction device can be straight
The collection that organic pollution is carried out as the absorption plant of organic pollution is connect, can also be processed further being made and be filled with the stone
The absorption plant of mertenyl water-oil separating foamed material；The foamed material can be the arbitrary shape such as square, circular.
During the plant running, air blower 12 and second gear pump 10, the DNAPL of water layer bottommost located underground are opened successively
Continually sucked in graphene-based water-oil separating foamed material 1, be then extracted ground and reach DNAPL collection vessels 14.
Due to the presence of air blower 12, the graphene-based surface of water-oil separating foamed material 1 can constantly rouse in DNAPL extractive process
Bubble, whole device then starts to extract the air that air blower 12 blasts when around foam without DNAPL, when neighbouring DNAPL exists
After being flowed under Action of Gravity Field in DNAPL collection wells 15, due to the lipophilic-hydrophobic property of material, DNAPL can preferentially be inhaled into foam
Then mentioned among material by second gear pumping in DNAPL collection vessels 15.This process is persistently carried out until all DNAPL
Mutually finished by extracting.Being introduced into of blower system, which ensure that in extractive process, extracts DNAPL under the conditions of having existing for DNAPL,
After DNAPL is extracted, underground water is not extracted, so as to realize serialization DNAPL high efficiente callback process.
DNAPL collects well 15 and is located at DNAPL regions part, and its borehole wall is porous self-supporting material, such as stainless (steel) wire structure
Into the circular borehole wall, or directly from surface drilling pvc pipe, PE pipe, steel pipe, ensure DNAPL can smoothly be flowed into
Device is collected in collection well to absorb and be enriched with.
Application examples 6
The extractive process that the application example pollutes according to the principle simulation soil of above-mentioned application examples 5 with the DNAPL in water table.
In model, beaker bottom liquid is dimethyl carbonate（The big organic matter of density ratio water, simulate DNAPL）, on beaker
Layer liquid is pure water（Simulated groundwater）；The graphene-based water-oil separating foamed material that embodiment 2 is prepared passes through oil
Pipe is connected with gear pump, and gear pump outlet is then inserted airway tube in foam by oil pipe and DNAPL coated lycopenes
（Insertion is deeply more shallow 3mm than oil pipe）, the other end of airway tube is connected with air pump.
Before extracting DNAPL, air pump is first opened, graphene-based water-oil separating foamed material is then impregnated into beaker bottom
DNAPL layers, gear pump is opened, DNAPL devices are brought into operation, and the simulation DNAPL of beaker bottom is continually extracted, without
Any moisture is extracted.After beaker bottom DNAPL is extracted, mechanical pump only extracts air without withdrawing moisture.
As a result：Water-bed DNAPL is fully drawn out, and hydrophobic foam continues bubbling without withdrawing moisture.Final effect beaker
Bottom is extracted in DNAPL collection vessels completely than the oil of water weight.
Claims (10)
- A kind of 1. graphene-based water-oil separating foamed material, it is characterised in that the contact angle of graphene-based water-oil separating foamed material For 120-155 degree.
- A kind of 2. preparation method of graphene-based water-oil separating foamed material according to claim 1, it is characterised in that bag Include following steps：1）Perforated foams are impregnated in graphene oxide water solution, further take out drying；2）By step 1）The material of acquisition is impregnated in the organic solution containing organohalosilanes, is further taken out drying and is obtained the graphite Alkenyl water-oil separating foamed material.
- 3. the preparation method of graphene-based water-oil separating foamed material according to claim 2, it is characterised in that step 1） In perforated foams be polyurethane foam, melamine foams, polyvinyl alcohol foam or foam metal；The foam metal is bubble Any one in foam nickel, foam copper, foamed aluminium or foamed iron, preferably nickel foam.
- 4. the preparation method of graphene-based water-oil separating foamed material according to claim 2, it is characterised in that step 1） In graphene oxide water solution in the concentration of graphene oxide be 0.01 ~ 1mg/mL.
- 5. the preparation method of graphene-based water-oil separating foamed material according to claim 2, it is characterised in that step 1） In time of dipping be 0.5 ~ 2h, preferably 1h；The temperature of drying be 50 ~ 70 DEG C, preferably 50 ~ 60 DEG C, the time of drying For 3 ~ 10h, preferably 3 ~ 8h.
- 6. the preparation method of graphene-based water-oil separating foamed material according to claim 2, it is characterised in that step 2） The mass concentration of middle organohalosilanes is 0.1 ~ 10wt%, and the organohalosilanes are organochlorosilane or organic iodine silane, organic Chlorosilane is octadecyl trichlorosilane alkane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, phenyl trichlorosilane, tertiary fourth Base dimethylchlorosilane, trim,ethylchlorosilane, dimethyldichlorosilane or methyl trichlorosilane, preferably octadecyl trichlorosilane Alkane, phenyl trichlorosilane, trim,ethylchlorosilane, dimethyldichlorosilane or methyl trichlorosilane, optimal is methyl trichlorosilane； Organic iodine silane is Iodotrimethylsilane.
- 7. the preparation method of graphene-based water-oil separating foamed material according to claim 2, it is characterised in that step 2） In time of dipping be 2 ~ 20min, preferably 2 ~ 10min；Drying temperature is 10 ~ 30 DEG C, preferably 20 ~ 30 DEG C；Drying Time is 1 ~ 5h, preferably 30 ~ 60min.
- 8. a kind of graphene-based water-oil separating foamed material according to claim 1 is in Oil Recovery and soil and underground Application in water organic pollution in-situ immobilization.
- A kind of 9. floating oil collecting device of the graphene-based water-oil separating foamed material comprising described in claim 1.
- 10. a kind of LNAPL original positions extraction device of graphene-based water-oil separating foamed material comprising described in claim 1 or DNAPL original positions extraction device.
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